Turfgrass Fungicide Formulation with Pigment

ABSTRACT

Oil-in-water fungicidal formulations are prepared having pigment dispersed therein, the pigment being stable within the oil-in-water emulsion as a result of the addition of suitable silicone surfactants and suitable emulsifiers. The formulations can be prepared either as a 2-pack formulation or as a single formulation. In the case of the single formulation polyethylene glycol is also added. In either case, the formulations show a synergistic effect through the addition of the pigment, the resulting formulations having an increased efficacy. Further, the formulations show a synergistic effect when mixed with conventional chemical fungicides, both being added in reduced amounts compared to recommended rates.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Patentapplication Ser. No. 61/075,821, filed Jun. 26, 2008 and U.S.Provisional Patent application Ser. No. 61/147,523, filed Jan. 27, 2009,the entirety of which are incorporated herein by reference.

FIELD OF THE INVENTION

Embodiments of the invention relate to oil-in water emulsions havingfungicidal properties when applied to turfgrass and more particularly,to oil-in-water emulsions having stable dispersions of pigment thereinfor enhancing fungicidal activity and for imparting color to theturfgrass when applied thereon.

BACKGROUND OF THE INVENTION

In Applicant's previous applications, such as in co-pendingUS-2005-0261379-A1, the entirety of which is incorporated herein byreference, the Applicant has previously described the use of anoil-in-water emulsion as means of controlling turf diseases. Adisadvantage may be that certain grasses such as varieties of bentgrassare sensitive to oil-in-water formulations which can often have theundesired effect of discolouring the grass especially under the heat ofsummer. Although the health of the plant is not negatively affected, thediscolouration can be problematic from an aesthetic perspective.

Pigment colorants, such as phthalocyanine compounds, are known to havebeen used in the turf industry, both in the presence and the absence offungicide. The known literature teaches the use of pigment color, suchas non-chlorinated copper phthalocyanine as a means of colouring thegrass or turf. One such example is US 2006/0293188 A1 to Norton (BayerCropscience LP), the entirety of which is incorporated herein byreference. Additional references include U.S. Pat. No. 5,336,661 toLucas, U.S. Pat. No. 5,643,852 to Lucas and U.S. Pat. No. 5,599,804 toMudge, the entirety of which are incorporated herein by reference.

Others references of interest include German application DE 2511077published in 1978, which teaches cobalt phthalocyanine as a colourant inthe absence of an acid. In an English abstract for JP 03-221576 toNippon Chemical Works, published Sep. 30, 1991, the disclosedformulation uses phthalocyanine “green”, an anionic dispersant, andacrylic acid ester-styrene and water.

Unfortunately, none of the teachings provide a solution for use ofpigment in oil-in-water emulsion systems as Applicant has found thatpigments, such as polychlorinated copper phthalocyanine, appear to clumpor coagulate and thereafter quickly fall out of suspension rendering theformulation unworkable.

Clearly, there is a need to provide an oil-in-water fungicidalformulation which contains a dispersion of pigment or colorant thereinin which the colorant remains stably dispersed for application toturfgrass.

SUMMARY OF THE INVENTION

Applicant has discovered that one can generate stable compositions ofpigment in a high oil-in-water emulsion environment by the addition of asmall amount of a silicone surfactant of a specific chemistry incombination with a small amount of an emulsifier of specific chemistry.The silicone surfactant and emulsifier are thought to act as dispersantsfor the pigment within the oil-based formulation, prior to dilution forforming the oil-in-water emulsion and in the final oil-in-wateremulsion. Formulations according to embodiments of the invention have anenhanced efficacy in treating turfgrass disease.

In addition, Applicant has found that the incorporation of a pigmentdispersed into the oil-in-water emulsion disclosed herein has asynergistic impact and improves the overall efficacy of disease controlof the active fungicidal components. At the same time, the amount of oilrequired to achieve adequate disease control can be reduced to abouthalf the amount of oil compared to the amount required if the oil isused alone, thus further reducing the possibility of phytoxicity.Further, discolouration issues which may occur on certain grasses, suchas varieties of bentgrass that are sensitive to oil-in-waterformulations especially under the heat of summer, are overcome byformulations prepared according to embodiments of the invention.

In addition, Applicant has determined that embodiments of the presentinvention have an unexpected synergistic effect when mixed withconventional chemical fungicides such as demethylation inhibitors (suchas propiconazole), methyl benzimidazole carbamate (such asthiophanate-methyl) and dicarboximide (such as iprodione). When mixedwith formulations according to embodiments of the invention, the dosageof such conventional chemical fungicides can be reduced significantly,such as to about 50% the recommended label rates, as well permittingsignificant reduction in the required dosage of the formulations of thepresent invention.

Advantageously, the present invention also acts to suppress certain turfinsects such as fall armyworms and sod webworms.

In a broad aspect of the invention, a fungicidal formulation forapplication to turfgrass comprises: an oil-in water emulsion comprisinga paraffinic oil, a suitable emulsifier and water; polychlorinated (CuII) phthalocyanine; and a silicone surfactant selected from the groupconsisting of trisiloxanes and silicone polyethers of Formula I

where: R═H, CH₃ or COCH₃; x=1 to 24; n=0 or 1; m=1,

wherein the polychlorinated (Cu II) phthalocyanine is maintained indispersion in the oil-in-water emulsion for delivery to turgrass.

In another broad aspect, a method for preparing the fungicidalformulation comprises: preparing a first composition having theparaffinic oil; and the suitable emulsifier selected from the groupconsisting of natural and synthetic alcohol ethoxylates, includingpolyoxyethylene (4 to 12) lauryl ether (C₁₂), polyoxyethylene (10) cetylether (C₁₆), polyoxyethylene (10) stearyl ether (C₁₈), polyoxyethylene(10) oleyl ether (C₁₈ monounsaturated), polyoxyethylene (2 to 11)C₁₂-C₁₅ alcohols, polyoxyethylene (3 to 9) C₁₁-C₁₄ alcohols,polyoxyethylene (9) C₁₂-C₁₄ alcohols; polyoxyethylene (11) C₁₆-C₁₈alcohols, and polyoxyethylene (20) C₁₂-C₁₅ alcohols; alcohol alkoxylatesincluding butyl polyoxyethylene/polyoxypropylene block copolymer; alkylpolysaccharides including C₈-C₁₁ alkylpolysaccharides; glycerol oleate;polyoxyethylene-polyoxypropylene block copolymers of MW 1100 to 11400and 10 to 80% EO; nonyl phenol ethoxylates including polyoxyethylene (2to 8) nonylphenol; polymeric surfactants including graft copolymer suchas polymethacrylic acid and acrylate with polyoxyethylene chains andrandom copolymer with ester and ether group; polyethylene glycolsincluding MW: 200 to 8000, MW: 400 PEG dioleate, and MW: 600 PEGdioleate; sorbitan fatty acid ester ethoxylates includingpolyoxyethylene (20) sorbitan tristearate, polyoxyethylene (20) sorbitanmonooleate, polyoxyethylene (5) sorbitan monooleate, and polyoxyethylene(20) sorbitan trioleate; and mixtures thereof; preparing a secondcomposition being and aqueous dispersion of the polychlorinated (Cu II)phthalocyanine; adding the silicone surfactant to one or both of thefirst and second compositions; and thereafter prior to use; and mixingan effective amount of the first composition with an effective amount ofthe second composition, the polychlorinated (Cu II) phthalocyanine beingdispersed and stable therein.

In another broad aspect, a method for preparing the fungicidalformulation comprises: preparing a single composition having theparaffinic oil; the suitable emulsifier selected from the groupconsisting of natural or synthetic alcohol ethoxylates includingpolyoxyethylene (4 to 7) lauryl ether (C₁₂); polyoxyethylene (10) cetylether (C₁₆); polyoxyethylene (2 to 11) C₁₂-C₁₅ alcohols; polyoxyethylene(3 to 9) C₁₁-C₁₄ alcohols; polyoxyethylene (9) C₁₂-C₁₄ alcohols;polymeric surfactants including graft copolymer such as polymethacrylicacid and acrylate with polyoxyethylene chains; and random copolymer withester and ether group; sorbitan fatty acid esters including sorbitantristearate; and sorbitan trioleate; and mixtures thereof; thepolychlorinated (Cu II) phthalocyanine being dispersed in oil; and thesilicone surfactant, wherein the silicone surfactant further comprisespolyethylene glycols (PEG) according to Formula (IV):

R₁—O—(CH₂—CH₂—O)_(n)—R₂  Formula (IV)

where: R₁═H or CH₂═CH—CH₂ or COCH₃.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graphical representation of the results of Example 7 showinga synergistic effect resulting from the addition of pigment to anoil-in-water fungicidal formulation prepared as a 2-pack formulation,permitting use of the formulation at rates lower than predicted rateswhen treating turfgrass infected with dollar spot disease;

FIG. 2 is a graphical representation of the results of Example 8 showingthe efficacy of the 2-pack fungicide applied at 5 gal/acre (non-aqueousportion) compared to conventional chemical fungicide, DACONIL® 2787,applied at the same rate for treating turfgrass infected with DollarSpot disease;

FIG. 3 is a graphical representation of the results of Example 9 showingthe efficacy of the 2-pack fungicide, applied at both 5 gal/acre(non-aqueous portion) and 10 gal/acre (non-aqueous portion), compared tothe chemical fungicide, DACONIL® 2787, for treating turfgrass infectedwith Dollar Spot disease;

FIG. 4 is a graphical representation of the results of Example 10showing the efficacy of weekly use of 2.5 gal/acre (non-aqueous portion)of 2-pack fungicide compared to an oil-in-water formulation without theaddition of the polychlorinated Cu (II) phthalocyanine pigment,emulsifier and silicone additives applied weekly at 5 gal/acre(non-aqueous portion);

FIG. 5 is a graphical representation of the results of Example 18comparing the efficacy of the 2-pack formulation, a 1-pack formulationand convention chemical fungicide DACONIL® Ultrex for treating turgrassinfected with Dollar Spot disease;

FIG. 6 is a picture of increased root length as a result of theapplication of a 2-Pack formulation prepared according to Example 6 whenapplied to a golf course fairway;

FIG. 7 is a picture of increased root length as a result of theapplication of a 2-Pack formulation, prepared according to Example 6, toareas of bentgrass;

FIG. 8 is a picture of increased root length as a result of theapplication of a 2-Pack formulation, prepared according to Example 6, toareas of bentgrass;

FIG. 9A is a graphical representation of the results of Example 21comparing the efficacy of a 2-pack formulation and a 2-pack formulationtank mixed at 50:50 with chemical fungicide BANNER MAXX™ for treatingturf infected with Dollar Spot disease;

FIG. 9B is a graphical representation of the results of Example 21showing a synergistic effect of a 2-pack formulation tank mixed at 50:50with chemical fungicide BANNER MAXX™ compared to the 2-pack formulationalone for treating turf infected with Dollar Spot disease, the residueperiod extending from 21 days to 28 days;

FIG. 10 is a graphical representation of the results of Example 22showing a synergistic effect of a 1-pack formulation tank mixed 50:50with chemical fungicide BANNER MAXX™ compared to the 1-pack formulationalone for treating turf infected with dollar spot disease;

FIG. 11 is a graphical representation of the results of Example 23illustrating the effectiveness of a 2-pack formulation with 50% of therecommended label rate of BANNER MAXX™ compared to the 2-packformulation alone, 50% of the recommended label rate of BANNER MAXX™alone and an untreated control for treating turf infected with Typhulaishikariensis;

FIG. 12 is a graphical representation of the results of Example 24illustrating the effectiveness of a 2-pack formulation with 50% of therecommended label rate of BANNER MAXX™ compared to the 2-packformulation alone, 50% of the recommended label rate of BANNER MAXX™alone and an untreated control for treating turf infected with Typhulaincarnate;

FIG. 13 is a graphical representation of the results of Example 25illustrating the effectiveness of a 2-pack formulation with 50% of therecommended label rate of BANNER MAXX™ compared to the 2-packformulation alone, 50% of the recommended label rate of BANNER MAXX™alone and an untreated control for treating turf infected withMicrodochium nivale;

FIG. 14 is a graphical representation of the results of Example 26comparing the efficacy of a 2-pack formulation enhanced with 50% of therecommended label rate of ROVRAL® Green GT to ROVRAL® Green GT at fulllabel rate alone and ROVRAL® Green GT applied alone at 50% of therecommended label rate for the control of Fusarium Patch disease onbentgrass;

FIG. 15 is a graphical representation of the results of Example 27comparing the efficacy of a 2-Pack formulation prepared according toExample 6 and applied at the full rate, conventional chemical fungicideCleary 3336™ Plus at the full recommended label rate, the 2-packformulation mixed 50:50 with Cleary 3336™ Plus, the 2-pack formulationalone at 50% of the recommended rate, and Cleary 3336™ Plus alone at 50%the recommended label rate, when applied to perennial ryegrass forcontrol of Gray Leaf Spot disease; and

FIG. 16 is a graphical representation of the results of Example 28illustrating a synergistic effect of the addition polychlorinated Cu(II)phthalocyanine when compared to oil/emulsifier alone and pigment alone,when compared to an untreated control.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Prior Art

Applicant has found that the addition of colorants or pigments, basedupon the teachings in the prior art, to oil-in-water emulsionformulations resulted in unstable dispersions of the pigment therein.

In the following Examples 1 through 3, polychlorinated Cu(II)phthalocyanine pigment (available from Sun Chemical as SUNSPERSE® Green7, ˜60% polychlorinated Cu (II) phthalocyanine dispersed in water or asPigment Green 7 powder available from Hercules Exports, Mumbai, India)was added to a synthetic isoparaffinic oil (N65DW available fromPetro-Canada, Calgary, AB, Canada), with or without polyoxyethyenelauryl ether, C₁₀ to C₁₆ alcohol ethoxylates, and glycerol oleate as anemulsifier (available as PC Emuls Green, from Petro-Canada, Calgary, AB,Canada) and was diluted in water to form the oil-in-water emulsionsuitable for application to turfgrass.

In each of Examples 1-3, the pigment coagulated or formed clumps whichrapidly separated out and/or resulted in phase separation of theformulations. Thus, the pigment did not remain dispersed in theformulations and therefore the formulations were not usable to reliablyand evenly impart color to turfgrass.

Example 1

-   -   a. 0.3 to 0.5 wt % polychlorinated Cu (II) phthalocyanine        (SUNSPERSE® Green 7)    -   b. 10 wt % synthetic isoparaffinic oil (N65DW)    -   c. 89.5 wt % water

Example 2

-   -   a. 0.3-0.5 wt % polychlorinated CU (II) phthalocyanine        (SUNSPERSE® Green 7)    -   b. 10 wt % isoparaffinic oil (N65DW)    -   c. 0.1 wt % emulsifier (PC Emuls Green)    -   d. 89.4 wt % water

Example 3

-   -   a. 0.5 wt % polychlorinated Cu (II) phthalocyanine (Pigment        Green 7 powder)    -   b. 10 wt % isoparaffinic oil (N65DW)    -   c. 0.1 wt % emulsifier (PC Emuls Green)    -   d. 89.4 wt % water

Embodiments of the Invention

As shown in Example 4, Applicant has found that the incorporation ofspecific silicone surfactants and emulsifier dispersants added to anoil-in-water emulsion, having a significant portion of oil therein andcontaining pigment, results in the pigment being stably dispersedtherein for application, such as by spraying, to turfgrass.

The non-aqueous portion of the oil-in-water portion is typically appliedat rates from about 1 gal/acre (0.093 L/100 m²) to about 15 gal/acre(1.395 L/100 m²). The total spray volume of the oil-in-water emulsion istypically from about 20 gal/acre (1.9 L/100 m²) to about 200 gal/acre(18.6 L/100 m²).

Example 4

A formulation according to an embodiment of the invention was preparedas follows:

-   -   a. 0.5 wt % polychlorinated Cu (II) phthalocyanine (SUNSPERSE®        Green 7)    -   b. 10 wt % isoparaffinic oil (N65DW)    -   c. 0.1 wt % emulsifier (PC Emuls Green)    -   d. 89.3 wt % water    -   e. 0.1 wt % silicone surfactant (Lambent MFF-199 SW)

An exemplary silicone super-wetting agent, such as Lambent MFF-199 SW(available from Lambent Technologies, a division of Petroferm, Inc.,Gurnee, Ill., USA. MFF-199-SW) is a silicone copolyol, containing ahydrogen end group and one pendant polyethylene oxide group and has anaverage molecular weight between 600 to 1000 Daltons.

Lambent MFF-199 is a totally different class of silicone oil compared tocommon linear or cyclic polydimethyl-siloxane. Lambent MFF-199 is atrisiloxane with an ethoxylated alkyl group having a hydrogen end group(H-End). The number of ethoxylation group is in the range of 1-20.

The suggested structure is as follows:

where: n=1-20 and average n=8

2-Pack Formulation

In an embodiment of the invention, a first composition (Pack A) isprepared containing the paraffinic oil and a suitable emulsifier. Asecond composition (Pack B) is prepared comprising a polychlorinated Cu(II) phthalocyanine. The polychlorinated Cu (II) phthalocyanine can beprovided as a powder dispersed in water or as a ready to use aqueousdispersion. A silicone surfactant, such as Lambent MFF 159-100 or MFF199 SW or other suitable silicone surfactant as described below can beadded entirely to Pack A or to Pack B. Alternatively, the siliconesurfactant can be split between Pack A and Pack B.

Immediately prior to use, an effective amount of each of Pack A and PackB are mixed together to form the fungicidal dispersion which is furtherdiluted in water to the desired concentration, as described below, fordelivery to turfgrass at a predetermined dosage rate.

More particularly, in embodiments of the invention, the effective amountof Pack A is mixed with some or all of the water which would be requiredto obtain a desired concentration so as to form an emulsion. Thereafter,the effective amount of Pack B and any remaining water are added to theemulsion and the mixture is delivered to turfgrass as an oil-in-wateremulsion at a predetermined dosage rate.

The silicone and emulsifier are selected to provide an intermolecularhydrophilic and lipophilic balance upon mixing of Pack A and Pack B soas to substantially prevent the polychlorinated Cu (II) phthalocyaninefrom clumping and rapidly separating out of suspension in the presenceof the oil phase during application to the turfgrass.

Suitable silicone surfactants comprise trisiloxanes or siliconepolyethers having a suitable alkoxy group with hydrogen end groups(H-capped), methyl end groups (CH₃ capped) or acetyl end groups (COCH₃capped) according to the following formula (I):

Where:

R═H; x=1 to 24; n=0; m=1; H-capped trisiloxane

R═H; x=1 to 24; n 1; m=1; H-capped silicone polyethers

R═CH₃; x=1 to 24; n=0; m=1; CH₃-capped trisiloxane

R═CH₃; x=1 to 24; n 1; m=1; CH₃-capped silicone polyethers

R═COCH₃; x=1 to 24; n=0; m=1; COCH₃-capped trisiloxane

R═COCH₃; x=1 to 24; n 1; m=1; COCH₃-capped silicone polyethers

Commercial preparations of the silicone surfactants above may or may notcontain small amounts of polyethylene glycols (PEG) or other lowmolecular weight polydimethyl siloxanes (PDMS).

In embodiments of the invention, silicone surfactant is added in a rangeof about 0.1 wt % to about 5 wt % in the non-aqueous portion of theoil-in-water emulsion.

In an embodiment of the invention, the silicone surfactant, added in anamount of about 2 wt % in the non-aqueous portion of the oil-in-wateremulsion, is an H-capped dimethyl methyl (polyethylene oxide) siliconepolymer having a molecular weight from 200-6000 as shown below inFormula (II):

where: n=2-70, the average n=44; m=2-16 and the average m=10.

Suitable emulsifiers are selected and added in amounts so as to generatea stable emulsion and to prevent phytotoxicity. The emulsifier is addedin a range from about 0.5 wt % to about 5 wt % in the non-aqueousportion of the oil-in-water emulsion. More particularly, in embodimentsof the invention, the emulsifier is added in a range from about 1 wt %to about 3 wt % in the non-aqueous portion of the oil-in-water emulsion.In an embodiment of the invention, the emulsifier is added at about 2 wt% in non-aqueous portion of the oil-in-water emulsion.

The emulsifier is selected from the group consisting of:

-   -   Alcohol ethoxylates (natural and synthetic) including        polyoxyethylene(4 to 12) lauryl ether (C12);        polyoxyethylene (10) cetyl ether (C16); polyoxyethylene (10)        stearyl ether (C18); polyoxyethylene (10) oleyl ether (C18        monounsaturated); polyoxyethylene (2 to 11) C12-C15 alcohols;        polyoxyethylene (3 to 9) C11-014 alcohols; polyoxyethylene (9)        C12-C14 alcohols; polyoxyethylene (11) C16-C18 alcohols; and        polyoxyethylene (20) C12-C15 alcohols;    -   Alcohol al koxylates including butyl        polyoxyethylene/polyoxypropylene block copolymer;    -   Alkyl polysaccharides including C₈-C₁₁ alkylpolysaccharides;    -   Glycerol oleate;    -   Polyoxyethylene-polyoxypropylene block copolymers of MW 1100 to        11400 and 10 to 80% EO;    -   Nonyl phenol ethoxylates including polyoxyethylene (2 to 8)        nonylphenol;    -   Polymeric surfactants including graft copolymer such as        polymethacrylic acid and acrylate with polyoxyethylene chains        and random copolymers with ester and ether groups;    -   Polyethylene glycols including MW: 200 to 8000; MW: 400 PEG        dioleate; and MW: 600 PEG dioleate; and    -   Sorbitan fatty acid ester ethoxylates including        polyoxyethylene (20) sorbitan tristearate; polyoxyethylene (20)        sorbitan monooleate; polyoxyethylene (5) sorbitan monooleate;        and polyoxyethylene (20) sorbitan trioleate.

Examples of 2-Pack Embodiment

In embodiments of the invention, a sufficient volume of Pack A was addedto a volume of water required to obtain a desired concentration in thefinal formulation and was mixed to form an emulsion. Sufficient Pack Bwas added to the emulsion to result in a fungicidal dispersion whichcomprised:

an effective amount of paraffinic oil, being about 5 wt %;

about 0.1 wt % emulsifiers;

about 0.3 wt % polychlorinated Cu (II) phthalocyanine; and

about 0.1 wt % silicone surfactant.

The fungicidal dispersion was sprayed onto turfgrass at a rate of fromabout 50 gal/acre (4.7 L/100 m²) to about 100 gal/acre (9.3 L/100 m²).

Example 5

In an example of the 2-Pack embodiment of the invention, the followingcompositions (Pack A and Pack B) were prepared and mixed together asdescribed to achieve the sprayable dispersion.

Pack A % by Purpose in Components Chemical Description Supplier Nameweight Formulation 1 N65DW Highly saturated paraffinic oils with aPetro-Canada 96 Active Ingredient carbon number distribution in therange of about C₁₆ to about C₃₅ 2 PC Emuls 1. Ethoxylated alcoholshaving primary Petro-Canada 2 Emulsifier Green C5-C20 carbon chains withan average of about 2 to about 7 ethoxylation groups 2. Glycerol Oleate3 Lambent Methyl (propylhydroxide, ethoxylated) Lambent Technologies 2Wetting MFF199 SW bis (trimethylsiloxy) silane Corp., Gumee IL USAagent/dispersant

Pack B Purpose in Components Chemical Description Supplier Name % byweight Formulation 1 SUNSPERSE ® 58% polychlorinated Cu(II) Sun ChemicalCorp 100 Colorant Green 7 phthalocyanine (C32HCl15CuN8) Performance(GCD9957) dispersed in water Pigment Cincinnati OH USA

In the embodiment of the invention described in Example 5, all of thesilicone surfactant was added to Pack A.

Example 6

In an example of the 2-Pack embodiment of the invention, the followingcomponents or compositions were prepared and mixed together as describedto achieve the sprayable dispersion.

Pack A % by Purpose in Components Chemical Description Supplier Nameweight Formulation 1 N65DW Highly saturated paraffinic oils with aPetro-Canada 98 Active carbon number distribution in the Ingredientrange of about C₁₆ to about C₃₅ 2 PC Emuls 1. Ethoxylated alcoholshaving Petro-Canada 2 Emulsifier Green primary C₅-C₂₀ carbon chains withan average of about 2 to about 7 ethoxylation groups 2. Glycerol Oleate

Pack B % by Purpose in Components Chemical Description Supplier Nameweight Formulation 1 SUNSPERSE ® 58% polychlorinated Cu(II) Sun ChemicalCorp 83.8 Colorant Green 7 phthalocyanine (C₃₂HCl₁₅CuN₈) PerformancePigment (GCD9957) dispersed in water Cincinnati, OH USA 2 LambentDimethyl, methyl (polyethylene Lambent 16.2 Wetting MFF159-10 oxide)silicone polymer Technologies Corp., agent/dispersant Gumee IL USA

In the embodiment of the invention described in Example 6, all of thesilicone surfactant was added to Pack B.

Examples 7 to 10 2-Pack Formulation

Examples 7 to 10 were performed using a formulation prepared accordingto Example 5.

Example 7 Comparison of the Efficacy of the 2-Pack Formulation to aFormulation Without Pigment

An embodiment of the invention was applied to creeping bentgrass(Agrostis stolonifera) at a close cut putting green height of 5 mm todetermine the efficacy of an embodiment of the invention to controldollar spot. Dollar spot is caused by Sclertinia Homeocarpa and is themost common disease requiring control on golf courses throughout most ofthe world.

The embodiment of the invention, applied to the turfgrass at 5 gal/acre(0.5 L/100 m²) of the non-aqueous portion of the oil-in-water emulsion,was compared to the use a higher concentration of oil-in-water emulsionwithout pigment, applied at 10 gal/acre (1 L/100 m²) of the non-aqueousportion of the oil-in-water emulsion, and an inoculated control. Theplots were inoculated with five strains of Sclertinia Homeocarpa, oneweek after initial chemical application.

The fungicides were applied in water at a total spray volume rate ofabout 129 gal/acre (12 L/100 m²) using a wheel-mounted compressed airboom sprayer at 140 kPa. Applications were made at 14 day intervals.Weekly counts of dollar spot infection were conducted over the 6 weekperiod.

Chemical Treatment List

Treatment Treatment Product per 100 m² No. of Applications IntervalFungicide with 465 mL 3 14 days pigment (2-pack) Fungicide without 930mL 3 14 days pigment

Conclusions

As shown in FIG. 1, acceptable control of dollar spot was achieved usingthe 2-pack fungicide at 5 gal/acre (0.5 L/100 m²) with the addition ofthe polychlorinated Cu (II) phthalocyanine pigment dispersion,emulsifier and silicone additives.

The use of 5 gal/acre (0.5 L/100 m²) of the non-aqueous portion of the2-pack fungicide formulation performed substantially the same as usingthe oil-in-water emulsion alone at 10 gal/acre (1 L/100 m²) of thenon-aqueous portion. The data suggests a synergistic effect resultingfrom the addition of pigment, permitting use of the formulation at rateslower than predicted rates.

An additional benefit of the lower treatment rate is the reducedpropensity for phytotoxicity which may be observed at high oil rates.

Example 8

A 2-Pack embodiment of the invention was applied to creeping bentgrass(Agrostis stolonifera) at a close cut putting green height of 5 mm todetermine the efficacy of an embodiment of the invention to controldollar spot. Close cut turf is highly susceptible to dollar spot.

The 2-pack embodiment of the invention was compared to a chemicalfungicide, DACONIL® 2787, also known as WEATHERSTIK™, available fromSyngenta Crop Protection Canada, Inc. Guelph, Ontario, Canada, and aninoculated control. The trials were conducted on 8 year old PENNCROSS®creeping bentgrass (Agrostis stolonifera). The treatments were appliedover a 7-week period and the turf and disease were monitored over a9-week period to examine residual effects and grass recovery. Arandomized complete block design having four replications was used andeach treatment plot measure 1 m×2 m. The plots were inoculated with fivestrains of Sclertinia Homeocarpa, one day after initial chemicalapplication.

Due to the close cutting of the turf in this example the diseasepressure was extreme. The fungicides were applied in water at a totalspray volume rate of 118 gal/acre (11 L/100 m²) using a wheel-mountedcompressed air boom sprayer at 140 kPa. Applications were made at 14 dayintervals for both the DACONIL® and the 2-pack formulation. Anadditional plot was treated with applications of the 2-pack formulationat 7 day intervals. Weekly counts of dollar spot infection wereconducted over the 7 week period.

Chemical Treatment List

No. of Treatment Treatment Product per 100 m² Applications IntervalDACONIL ® 2787  95 mL 4 14 days 2-pack fungicide 465 mL 4 14 days 2-packfungicide 465 mL 7  7 days

Results

As shown in FIG. 2, low levels of dollar spot disease were present onall of the plots at the start of the trial. Nearing the end of thetrial, the disease levels in the control exceeded 100 spots per plot onthe inoculated areas. All three chemical treatments showed significantsuppression of dollar spot disease when compared to the control. Thesuppression of disease continued for about two weeks following the lastapplication.

It was noted that when applied weekly, the 2-pack formulation performedsubstantially better than the 2-pack formulation or the DACONIL® appliedat the recommended rate of biweekly. One of skill in the art wouldrecognize therefore that, in cases of extreme dollar spot disease,efficacy of the 2-pack formulation is improved if applied morefrequently.

Phytotoxicity was not observed in any of the treatments.

Conclusions

The 2-pack fungicide, applied at 5 gal/acre (0.5 L/100 m²) of thenon-aqueous portion performed substantially the same as the chemicalfungicide, DACON ILO 2787.

In cases of extreme disease pressure the 2-pack formulation should beapplied more frequently.

Example 9

An embodiment of the invention was applied to creeping bentgrass(Agrostis stolonifera) at a fairway height of 11 mm to determine theefficacy of an embodiment of the invention to control dollar spot.Dollar spot is caused by Sclertinia Homeocarpa and is the most commondisease requiring control on golf courses throughout most of the world.

The embodiment of the invention was compared to a chemical fungicide,DACONIL® 2878, also known as WEATHERSTIK™, available from Syngenta CropProtection Canada, Inc. Guelph, Ontario, Canada, and an inoculatedcontrol. The trials were conducted on 13 year old PENNCROSS® creepingbentgrass (Agrostis stolonifera). The treatments were applied over a6-week period and the turf and disease were monitored to examineresidual effects and grass recovery. A randomized complete block designhaving four replications was used and each treatment plot measure 1 m×2m. The plots were inoculated with five strains of Sclertinia Homeocarpa,one week after initial chemical application.

The fungicides were applied in water at a total spray volume rate of 129gal/acre (12 L/100 m²) using a wheel-mounted compressed air boom sprayerat 140 kPa. Applications were made at 14 day intervals. Weekly counts ofdollar spot infection were conducted over the 6 week period.

Chemical Treatment List

No. of Treatment Treatment Product per 100 m² Applications IntervalDACONIL ® 2787  95 mL 3 14 days 2-pack fungicide 465 mL 3 14 days 2-packfungicide 930 mL 3 14 days

Results

As shown in FIG. 3, dollar spot disease was present on all of the plotsat the start of the trial. All three treatments showed significantsuppression of dollar spot disease when compared to the control. Thesuppression of disease continued for about two weeks following the lastapplication.

Phytotoxicity was not observed in any of the treatments.

Conclusions

The 2-pack fungicide, applied at both 5 gal/acre (0.5 L/100 m²) of thenon-aqueous portion and 10 gal/acre (1 L/100 m²) of the non-aqueousportion, performed substantially the same as the chemical fungicide,DACON ILO 2787.

Example 10

An embodiment of the 2-pack formulation was used to treat dollar Spot onPoa Trivialis (rough stalk bluegrass) overseeded Bermudagrass plot cutat putting green height. The 2-pack formulation was applied at 2.5gal/acre (0.2 L/100 m²) of the non-aqueous portion and was compared to aformulation prepared without the pigment, the silicone surfactant andthe particular emulsifier and which was applied at 5 gal/acre (0.5 L/100m²) of the non-aqueous portion and to an untreated control.

The formulations were applied using a CO₂ backpack boom sprayercalibrated to deliver products in 2 gallons of water per 1000 sq ft (8L/100 m²) through two 8003 TEEJETO flat fan nozzles.

The turfgrass plots were divided into 4 blocks and treatments wereassigned in a randomized complete block design. The plots wereinoculated with 1 L of wheat seed infested with Sclerotinia homoeocarpa.Fungicide formulations were applied weekly for 8 weeks.

Having reference to FIG. 4, dollar spot counts were made throughout the8 week period.

Conclusions:

Acceptable control of dollar spot was obtained through weekly use of 2.5gal/acre (0.2 L/10 m²) of the non-aqueous portion of 2-pack fungicidewhich represents approximately one half the amount required to achievethe same result using a formulation without the addition of thepolychlorinated Cu (II) phthalocyanine pigment dispersion, emulsifierand silicone additives (5 gal/acre (0.5 L/100 m²) of the non-aqueousportion, weekly).

Advantageously, the use of a lower treatment rate reduces the propensityfor phytotoxicity which may be observed at high rate oil rates.

Example 11

Example 11 was performed using a formulation prepared according toExample 6.

Kentucky bluegrass was mowed three times per week at a cutting height of2 inches. Applications of the 2-pack formulation were made at 14-dayintervals beginning April 10. Assessment of Spring leaf spot orMelting-out disease was made using a “0 to 10” severity index, where 10is equivalent to greater than 90% symptomatic turf area.

For the purposes of comparison to conventional treatment, DACONIL®ULTREX, available from Syngenta Crop Protection Canada, Inc. Guelph,Ontario, Canada, was used as a control.

Results

Application rate Disease Severity Treatment (oz/1000 ft²) 14-May 22-May28-May 4-Jun Untreated 2.7ab 4.3a 5.3a 6.7a 2-pack 21.75 0.0e 0.3ef0.3ef 0.3hi DACONIL ® Ultrex 3.2 0.0e 0.0f 0.0f 0.0i LSD (P = 0.05) 1.450.96 1.38 1.28 Std Deviation 0.89 0.59 0.85 0.78 Means in a row followedby the same letter are not significantly different (alpha = 0.05) usingLSD test

No phytotoxicity was observed in any treatment plot.

Conclusions:

The 2-Pack formulation, used at 7.5 gal/acre (0.7 L/100 m²) of thenon-aqueous portion) provided excellent disease control.

1-Pack Formulation

In another embodiment of the invention, Applicant has surprisingly foundthat pigment, such as polychlorinated Cu (II) phthalocyanine, can beprepared in a single, stable dispersion in an oil-based fungicidalcomposition, prior to dilution in water to form a sprayable dispersion.Thus, the user does not need to handle two separate components forpreparing a stable fungicidal application.

More specifically, the pigment is dispersed in a compatible oil, such asa paraffinic oil or the same paraffinic oil as is used used to providethe fungicidal properties as described in embodiments of the invention,for additional to the formulation. Use of specific silicone surfactantand emulsifier chemistries stabilizes the colorant in the oil-basedcomposition.

In examples of the 1-pack formulation, polychlorinated Cu(II)phthalocyanine is dispersed in a paraffinic oil, such as N65DW(available from Petro-Canada) to provide about 18% polychlorinatedCU(II) phthalocyanine (SUNSPERSE® EXP 006-102, available from SunChemical Corp. Performance Pigments, Cincinnati, Ohio USA) prior tomixing with the remaining constituents.

In embodiments of the invention, the 1-pack formulation comprisessilicone surfactant, emulsifier and polyethylene glycols which areselected to provide an intermolecular hydrophilic and lipophilic balancewithin the fungicidal formulation so as to substantially prevent thepolychlorinated Cu(II) phthalocyanine from separating out of suspensionduring application to the turf grass.

Applicant believes that suitable silicone surfactants are thosepreviously identified for the 2-pack formulation, as described inFormula (I). In embodiments of the invention the silicone surfactantsare H-capped, CH₃-capped and COCH₃-capped trisiloxanes. In an embodimentof the invention, the silicone is an H-capped trisiloxane as shown belowin Formula (III):

Where: n=1-24, average n=8-10.

Suitable emulsifiers for the 1-Pack formulation are selected from thefollowing:

-   -   Alcohol ethoxylates (natural and synthetic) including        polyoxyethylene (4 to 7) lauryl ether (C12);        polyoxyethylene (10) cetyl ether (C16); polyoxyethylene (2        to 11) C12-C15 alcohols; polyoxyethylene (3 to 9) C11-C14        alcohols; polyoxyethylene (9) C12-C14 alcohols;    -   Polymeric surfactants including graft copolymer such as        polymethacrylic acid and acrylate with polyoxyethylene chains        and random copolymers with ester and ether groups; and    -   Sorbitan fatty acid esters including sorbitan tristearate and        sorbitan trioleate.

The emulsifier is added to the formulation in a range of about 0.5 wt %to about 5 wt % in the non-aqueous portion of the formulation.

In embodiments of the invention, Applicant has noted that the siliconesurfactants used typically comprise 10-30% polyethylene glycols (PEG)according to Formula (IV) shown below.

R₁—O—(CH₂—CH₂—O)_(n)—R₂  Formula (IV)

Where:

R₁═H or CH₂═CH—CH₂ or COCH₃

R₂═H or CH₂═CH—CH₂ or COCH₃

n≧1

In embodiments of the invention, the PEG has a low molecular weight,typically about 300 to about 1500 Daltons. In embodiments of theinvention, the PEG is a low molecular weight polyethylene glycol allylether. In embodiments of the invention, the PEG is a low molecularweight polyethylene glycol mono-allyl ether having an average molecularweight of from about 300 to about 600 Daltons and having from 1 to 20moles of ethylene glycol with an average ethoxylation (EO) of 8 to 10.

Examples 12 to 14 1-Pack Formulations Example 12

28 wt % SUNSPERSE® EXP 006-102 containing 18 wt % polychlorinated Cu(II)phthalocyanine, dispersed in N65DW;

2 wt % silicone surfactant according to Formula (I) where: m=1, n=0,X=1-24 (average 8-10) and R═H; and PEG according to Formula (IV) where:R₁═CH₂=CH—CH₂, R₂═H and n=1-20 with an average n=8 (Lambent MFF199);

2 wt % polyoxyethylene (11) C₁₆₋₁₈ alcohols such as LUTENSOL® AT11available from BASF; and

68 wt % N65DW.

Example 13

28 wt % SUNSPERSE® EXP 006-102 containing 18 wt % polychlorinated Cu(II)phthalocyanine, dispersed in N65DW;

2 wt % silicone surfactant according to Formula (I) where: m=1, n=0,X=1-24 (average 8-10) and R═H; and PEG according to Formula (IV) where:R₁═CH₂=CH—CH₂, R₂═H and n=1-20 with an average n=8 (Lambent MFF199);

2 wt % sorbitan tristearate such as SPAN65 available from Uniqema orS-MAZ® 65K available from BASF; and

68 wt % N65DW.

Example 14

28 wt % SUNSPERSE® EXP 006-102 containing 18 wt % polychlorinated Cu(II)phthalocyanine, dispersed in N65DW;

1.8 wt % silicone surfactant as described in Formula (I) where m=1, n=0,X=1-24 (average 8-10) and R═COCH₃, and Polyethylene Glycols as describedin Formula (IV) where R₁═CH₂=CH—CH₂ or COCH₃, R₂═COCH₃ (SYLGARD® 309,available from Dow Corning, USA)

0.2% Polyethylene Glycols as described in Formula (IV) whereR₁═CH₂=CH—CH₂, R₂═H (Polyglykol A500, available from Clariant);

2 wt % polyoxyethylene (11) C₁₆₋₁₈ alcohols, such as LUTENSOL® AT11available from BASF; and

68 wt % N65DW.

The formulations disclosed in Examples 12-14 were further diluted to 6%in water prior to application to the turfgrass. The resultingoil-in-water formulations comprised:

about 5 wt % paraffinic oil;

about 0.12 wt % emulsifier;

about 0.3 wt % polychlorinated Cu(II) phthalocyanine;

about 0.1 wt % silicone surfactant;

about 0.01-0.03 wt % polyethylene glycol; and

the balance being water.

The resulting oil-in-water emulsion/pigment dispersions were found to bestable until applied, typically within one day and can be applied toturfgrass. The oil-in-water emulsions were applied at a conventionaltotal spray volume rate of about 50 gal/acre (4.7 L/100 m²) to about 100gal/acre (9.3 L/100 m²).

Examples 15-17

Additional testing was performed to determine the stability of 1-packformulations without the presence of silicone surfactant and/or PEG.

In Examples 15-17, the formulations were further diluted to 6% in waterto form the oil-in-water emulsion prior to application to turfgrass.

Example 15

A 1-pack formulation was prepared with neither silicone surfactant norPEG according to the following formula:

28 wt % SUNSPERSE® EXP 006-102 containing 18 wt % polychlorinated Cu(II)phthalocyanine, dispersed in N65DW;

2 wt % polyoxyethylene (11) C₁₆₋₁₈ alcohols such as LUTENSOL® AT11available from BASF; and

70% N65DW.

Example 16

A 1-pack formulation was prepared with insufficient PEG according to thefollowing formula:

28 wt % SUNSPERSE® EXP 006-102 containing 18 wt % polychlorinated Cu(II)phthalocyanine, dispersed in N65DW;

2 wt % silicone surfactant as described in Formula (I) where m=1, n=0,X=1-24 (average 8-10) and R═H(SILTECH® SILSURF® A008-UP);

2 wt % polyoxyethylene (11) O₁₆₋₁₈ alcohols such as LUTENSOL® AT11available from BASF; and

68% N65DW.

Example 17

A 1-pack formulation was prepared without silicone surfactant accordingto the following formula:

28 wt % SUNSPERSE® EXP 006-102 containing 18 wt % polychlorinated Cu(II)phthalocyanine, dispersed in N65DW;

2 wt % Polyethylene Glycols as described in Formula (IV) whereR₁═CH₂=CH—CH₂, R₂═H (Polyglykol A500, available from Clariant);

2 wt % polyoxyethylene (11) C₁₆₋₁₈ alcohols such as LUTENSOL® AT11available from BASF; and

68% N65DW.

Results:

The pigment aggregated and fell out of suspension in all of theformulations tested in Examples 15-17, rendering the formulationsunusable.

Conclusions:

As shown in Examples 12-17, without both silicone surfactant andsufficient amounts of PEG, the resulting 1-pack formulations, diluted toform oil-in-water emulsions, are not stable and are therefore not usablefor turf application.

As demonstrated in Examples 12-17, the presence of silicone surfactantsand polyethylene glycols improve the stability and dispersibility of the1-Pack formulation resulting in a commercially viable fungicidaldispersant for turf application and management of disease therein.

Example 18

Embodiments of the 1-pack and 2-pack formulations, according to theinvention, and a conventional fungicide, DACONIL® Ultrex, were used totreat dollar Spot on Poa Trivialis (rough stalk bluegrass) overseededBermudagrass plot cut at putting green height. As with Example 10, theformulations were applied with a CO₂ backpack boom sprayer calibrated todeliver products in 2 gallons of water per 1000 sq ft (8 L/100 m²)through two 8003 TEEJET® flat fan nozzles.

The plots were divided into 4 blocks and treatments were assigned in arandomized complete block design. The plot was inoculated with 1 L ofwheat seed infested with Sclerotinia homoeocarpa. The formulations wereapplied biweekly for 8 weeks.

As shown in FIG. 5, dollar spot counts were made throughout the 8 weekperiod.

Conclusions:

Both the 1-pack and 2-pack formulations had substantially the sameefficacy as the DACONIL® Ultrex.

Example 19

A 2-Pack formulation was prepared according to Example 6 an applied on afairway and an area of rough at the Saginaw Golf Course in Cambridge,Ontario, Canada for an 8 week period using a 14-day applicationinterval.

At the end of 8 weeks, core samples of the treated and untreated areaswere obtained to compare root development.

Results

As shown in FIG. 6, the grass on the treated areas (left) was muchdenser and healthier than on the untreated areas (right). Further, thetreated areas had a darker green color than the untreated areas.

It was found that the roots of the bentgrass on the treated area werelonger by approximately twice the length of the roots of the untreatedbentgrass. Further, the roots were observed to be denser than the rootsof untreated bentgrass.

Conclusions:

The 2-Pack and 1-Pack formulations promote the growth of bentgrass andbluegrass.

Example 20

Having reference to FIGS. 7 and 8, areas of bentgrass were treated usinga 2-Pack formulation prepared according to Example 6. Seven (7) coresamples were randomly taken from treated areas and from untreated areasfor comparison. The core samples were soaked overnight in water in aglass tray. Subsequently, soil from the roots was washed away with waterto reveal the root structure, as shown in FIGS. 7 and 8 and summarizedin Table A below.

Results

TABLE A Untreated root Core sample # length (inches) Treated root length(inches) 1 3.5 5.5 2 3.0 4.5 3 3.75 4.0 4 2.75 5.25 5 2.75 4.5 6 2.754.75 7 4.25 4.75 Average 3.25 4.75

Conclusions:

On the average, the root length of the treated bentgrass isapproximately 50% longer than that of the untreated bentgrass. Furtherit was noted that the root mass was considerably greater for the treatedbentgrass.

Enhanced Formulation

Applicant has determined that embodiments of the present invention havea surprising synergistic effect when mixed with some conventionalsystemic chemical fungicides selected from the group consisting ofdemethylation inhibitors (such as propiconazole), methyl benzimidazolecarbamate (such as thiophanate-methyl) and dicarboximide (such asiprodione). As an example, a suitable propiconazole fungicide is BANNERMAXX™ (available from Syngenta Crop Protection Canada, Inc. Guelph,Ontario, Canada), a thiophanate-methyl fungicide is Cleary 3336™(available from Cleary Chemical Corporation, Dayton, N.J., USA) and aniprodione fungicide is ROVRAL® Green (available from Bayer EnvironmentalScience-Canada, Guelph, Ontario, Canada).

Applicant has found however that, despite predictions to the contrary,the synergistic effect was not observed with all conventional chemicalfungicides, such as some contact fungicides, one of which waschlorothalonil (such as DACONIL® Ultrex, available from Syngenta CropProtection Canada, Inc. Guelph, Ontario, Canada).

As shown in the following additional examples for treatment of DollarSpot, snow moulds and gray leaf spot, mixing an embodiment of thepresent invention at half the predicated recommended label rate in equalparts with certain conventional chemical fungicides at half the amountof the label rate resulted in an equivalent or improved efficacy of themixture when compared to each of the fungicides used alone at full labelrate.

As one of skill would understand and as taught by Burpee and Latin,Plant Disease Vol. 92 No. 4, April 2008, pp 601-606., knowing that theefficacy of fungicides is not additive, the addition of half the labelrate of each of the two fungicidal formulations would not conventionallybe thought to result in high efficacy. Surprisingly this was not thecase with embodiments of the present invention. Mixtures of formulationsof the present invention and certain conventional chemical fungicides,at rates not thought to be useful, resulted synergistically in a highlyefficacious formulation.

Applicant believes that the amount of formulations according toembodiments of the invention can be reduced to a range from about 25% toabout 75% of the amount used if used alone, when mixed with theconventional chemical fungicide, also reduced to from about 25% to about75% of the recommended label rate.

Examples 21 and 22

Examples 21 and 22 illustrate results of use of the 1-pack formulation,the two pack formulation and the enhanced formulation on the treatmentof Dollar Spot on Poa Trivialis (rough stalk bluegrass) cut at puttinggreen height.

Example 21

Having reference to FIGS. 9A and 9B, the 2-pack formulation was tankmixed at 50:50 with chemical fungicide BANNER MAXX™ and applied to turfinfected with dollar spot disease.

The mixture of the 2-pack fungicide and the chemical fungicide exhibiteda synergistic effect compared to using either of the fungicides alone.As shown in FIG. 9B, the residue period can be extended from 21 days to28 days.

Example 22

Having reference to FIG. 10, the 1-pack formulation was tank mixed 50:50with chemical fungicide BANNER MAXX™ and applied to turf infected withdollar spot disease.

The 1-pack formulation with the addition of chemical fungicide exhibiteda synergistic effect when compared to use of the 1-pack formulation orBANNER MAXX™ alone, when applied at the full label rate.

Examples 23-25

Embodiments of the invention were mixed 50:50 with conventional chemicalfungicide BANNER MAXX™ to form an enhanced formulation and were appliedto creeping bentgrass (Agrostis stolonifera) at fairway height which wasinfected with a variety of snowmolds.

An enhanced formulation containing the 2-pack formulation and chemicalfungicide was compared to use of the fungicides alone. BANNER MAXX™ wasapplied at 50% the recommended label rate for comparison to the enhancedformulation.

Example 23

As shown in FIG. 11, the effectiveness of the enhanced formulation wascompared to the 2-pack formulation, 50% of the recommended label rate ofBANNER MAXX™ alone and an untreated control for treating turf infectedwith Typhula ishikariensis.

Example 24

As shown in FIG. 12, the effectiveness of the enhanced formulation wascompared to the 2-pack formulation, 50% of the recommended label rate ofBANNER MAXX™ alone and an untreated control for treating turf infectedwith Typhula incarnata.

Example 25

As shown in FIG. 13, the effectiveness of the enhanced formulation wascompared to the 2-pack formulation, 50% of the recommended label rate ofBANNER MAXX™ alone and an untreated control for treating turf infectedwith Microdochium nivale.

Conclusions:

It is clear from Examples 23-25 that use of the enhanced formulationcomprising 50% of the recommended rate of an embodiment of the inventionand 50% of the recommended label rate of BANNER MAXX™ is as effective,or more effective, than using either the 2-pack formulation or thechemical fungicide alone.

Example 26

A 2-Pack formulation was prepared according to Example 6 using half therecommended rate (i.e. 232.5 ml per 100 m² for the non-aqueous portion)and was mixed with a commercial fungicide ROVRAL® Green GT (availablefrom Bayer Environmental Science-Canada, Guelph, Ontario, Canada) at 50%the recommended label rate (i.e., applied at 125 ml per 100 m²) to formthe enhanced formulation.

The enhanced formulation was applied to creeping bentgrass (Agrostisstolonifera) cut to greens height for the control of Fusarium Patchdisease. ROVRAL® Green GT was also applied alone at 50% the recommendedrate ((i.e., applied at 125 ml per 100 m²) for comparison.

The treatments were applied over a 6-week period and disease wasmonitored weekly.

Conclusions:

As shown in FIG. 14, the enhanced formulation (“PC2 50%+ROVRAL® Green GT50%”) provided significant suppression of injury by Fusarium Patchdisease.

Example 27

One half (50%) of the recommended rate of a 2-Pack formulation (i.e., at2.5 gal per acre of the non-aqueous portion), prepared according toExample 6, was mixed 50:50 with a conventional chemical fungicide Cleary3336™ Plus at 50% the recommended rate (i.e., at 2 oz per 1000 ft²).

The enhanced formulation (PC2, ½ rate+Cleary 3336™ Plus, ½ rate), aswell as the individual formulations at full rate and at half rate, wereapplied to perennial ryegrass cut to fairway height for control of GrayLeaf Spot disease.

Conclusions:

As shown in FIG. 15, the enhanced formulation provided excellent controlof Gray Leaf Spot disease on Ryegrass.

Synergistic Effect of the Oil/Emulsion and Pigment Dispersion Example 28

As shown in FIG. 16, Applicant believes that in all formulationsaccording to embodiments of the invention, the addition of thepolychlorinated Cu(II) phthalocyanine has a synergistic effect whencompared to oil/emulsifier alone or pigment alone, when compared to anuntreated control.

Turf infected with Dollar Spot disease was treated with 10%oil/emulsifier alone, 0.5% SUNSPERSE® Green 7 alone and an embodiment ofthe invention comprising both 10% oil/emulsifier and 0.5% SUNSPERSE®Green 7.

Conclusions:

Clearly, it appears that addition of pigment to the fungicidal oilcomponent enhances the fungicidal properties of the dispersion.

Use of Embodiments of the Invention for Controlling Additional Pests inTurfgrass Example 29 Fall Armyworms

The efficacy of an embodiment of the 2-pack formulation againstdifferent larval stages of fall armyworms (Spodoptera frugiperda) wasdetermined under laboratory conditions. Embodiments of the inventionwere compared to a conventional pesticide Cyfluthrin.

Methods:

-   1) Larvae were obtained from Benzon Research Inc.-   2) 5 larvae/container and 3 containers=1 replication-   3) Treatments=1) Control    -   2) 2-pack formulation at 5% dilution    -   3) Cyfluthrin (insecticide), Al=0.75%, 3 fl oz/gal H₂O (22 mL/L)-   4) Container=760 ml plastic bowl with lid containing moist filter    paper on bottom and grass clippings-   5) St. Augustinegrass clippings dipped into respective fungicide    treatment, drained to dry and put into container-   6) Hold 4 days at 25° C. and measure survival-   7) 7 replications of small larvae (2-10 mm) tested-   8) 6 replications of medium larvae (11-20 mm) tested-   9) 6 replications of large larvae (21-30 mm) tested-   10) Statistical analysis=Least Significant Difference (LSD) test

Results:

Fall army Mean survival^(a) worms Larvae control Cyfluthrin 2-packformulation Small 3.86 A 0 B 0.43 B Medium 3.50 A 0 B 1.17 B Large 3.00A 0 B 2.50 A ^(a)Means in a row followed by the same letter are notsignificantly different (alpha = 0.05) using LSD test.

Conclusions:

The data indicates that embodiments of the 2-pack formulation areeffective to kill small and medium larvae of fall army worms.

Tropical Sod Webworms

Similar testing was conducted to determine the efficacy of embodimentsof the 2-pack formulation to kill all sizes larvae (small, medium andlarge) of tropical sod webworms.

Sodweb Mean survival^(a) worms Larvae control Cyfluthrin PC Small 3.0 A  0 B 0.3 B Medium 4.8 A   0 B   0 B Large 4.0 A 0.3 B 1.0 B ^(a)Meansin a row followed by the same letter are not significantly different(alpha = 0.05) using LSD test.

Conclusions:

The data indicates that embodiments of the 2-pack formulation areeffective to kill small, medium and large larvae of tropical sodwebworms.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:
 1. A fungicidal formulationfor application to turfgrass comprising: an oil-in-water emulsioncomprising a paraffinic oil, a suitable emulsifier and water;polychlorinated (Cu II) phthalocyanine; and a silicone surfactantselected from the group consisting of trisiloxanes and siliconepolyethers of Formula I

where: R═H, CH₃ or COCH₃; x=1 to 24; n=0 or 1; m=1, wherein thepolychlorinated (Cu II) phthalocyanine is maintained in dispersion inthe oil-in-water emulsion for delivery to turgrass.
 2. The fungicidalformulation of claim 1 wherein, the polychlorinated (Cu II)phthalocyanine is dispersed in water; and the emulsifier is selectedfrom the group consisting of natural and synthetic alcohol ethoxylates,including polyoxyethylene(4 to 12) lauryl ether (C₁₂₋), polyoxyethylene(10) cetyl ether (C₁₆), polyoxyethylene (10) stearyl ether (C₁₈),polyoxyethylene (10) oleyl ether (C₁₈ monounsaturated), polyoxyethylene(2 to 11) C₁₂-C₁₅ alcohols, polyoxyethylene (3 to 9) C₁₁-C₁₄ alcohols,polyoxyethylene (9) C₁₂-C₁₄ alcohols; polyoxyethylene (11) C₁₆-C₁₈alcohols, and polyoxyethylene (20) C₁₂-C₁₅ alcohols; alcohol alkoxylatesincluding butyl polyoxyethylene/polyoxypropylene block copolymer; alkylpolysaccharides including C₈-C₁₁ alkylpolysaccharides; glycerol oleate;polyoxyethylene-polyoxypropylene block copolymers of MW 1100 to 11400and 10 to 80% EO; nonyl phenol ethoxylates including polyoxyethylene (2to 8) nonylphenol; polymeric surfactants including graft copolymer suchas polymethacrylic acid and acrylate with polyoxyethylene chains andrandom copolymer with ester and ether group; polyethylene glycolsincluding MW: 200 to 8000, MW: 400 PEG dioleate, and MW: 600 PEGdioleate; sorbitan fatty acid ester ethoxylates includingpolyoxyethylene (20) sorbitan tristearate, polyoxyethylene (20) sorbitanmonooleate, polyoxyethylene (5) sorbitan monooleate, and polyoxyethylene(20) sorbitan trioleate; and mixtures thereof.
 3. The fungicidalformulation of claim 1 wherein the polychlorinated (Cu II)phthalocyanine is dispersed in oil; the emulsifier is selected from thegroup consisting of natural or synthetic alcohol ethoxylates includingpolyoxyethylene(4 to 7) lauryl ether (C₁₂); polyoxyethylene (10) cetylether (C₁₆); polyoxyethylene (2 to 11) C₁₂-C₁₅ alcohols; polyoxyethylene(3 to 9) C₁₁-C₁₄ alcohols; polyoxyethylene (9) C₁₂-C₁₄ alcohols;polymeric surfactants including graft copolymer such as polymethacrylicacid and acrylate with polyoxyethylene chains; and random copolymer withester and ether group; sorbitan fatty acid esters including sorbitantristearate; and sorbitan trioleate; and mixtures thereof; and thesilicone surfactant comprises polyethylene glycols (PEG) according toFormula (IV):R₁—O—(CH₂—CH₂—O)_(n)—R₂  Formula (IV) where: R₁═H or CH₂═CH—CH₂ orCOCH₃.
 4. The fungicidal formulation of claim 1 wherein a non-aqueousportion of the oil-in-water emulsion is delivered to the turfgrass in arange of about 1 gal/acre (0.093 L/100 m²) to about 15 gal/acre (1.395L/100 m²), a total spray volume of the oil-in-water emulsion being in arange of about 20 gal/acre (1.86 L/100 m²) to about 200 gal/acre (18.6L/100 m²).
 5. The fungicidal formulation of claim 1 wherein the siliconesurfactant is added in a range from about 0.1 wt % to about 5 wt % inthe non-aqueous portion of the oil-in-water emulsion.
 6. The fungicidalformulation of claim 1 wherein the emulsifier is added in a range fromabout 0.5 wt % to about 5 wt % in the non-aqueous portion of theoil-in-water emulsion.
 7. The fungicidal formulation of claim 1 whereinthe polychlorinated (Cu II) phthalocyanine is added in a range of about1 wt % to about 10 wt % in the non-aqueous portion of the oil-in-wateremulsion.
 8. The fungicidal formulation of claim 1 further comprising achemical fungicide selected from the group consisting of a demethylationinhibitor, methyl benzimidazole carbamate and dicarboximide, wherein thechemical fungicide is present at about 25% to about 75% of a recommendedlabel rate in the oil-in-water emulsion; and a non-aqueous portion ofthe fungicidal formulation of claim 1 is present at about 25% to about75% of a recommended rate in the oil-in-water emulsion.
 9. A method forpreparing the fungicidal formulation of claim 1 comprising: preparing afirst composition having the paraffinic oil; and the suitable emulsifierselected from the group consisting of natural and synthetic alcoholethoxylates, including polyoxyethylene(4 to 12) lauryl ether (C₁₂),polyoxyethylene (10) cetyl ether (C₁₆), polyoxyethylene (10) stearylether (C₁₈), polyoxyethylene (10) oleyl ether (C₁₈ monounsaturated),polyoxyethylene (2 to 11) C₁₂-C₁₅ alcohols, polyoxyethylene (3 to 9)C₁₁-C₁₄ alcohols, polyoxyethylene (9) C₁₂-C₁₄ alcohols; polyoxyethylene(11) C₁₆-C₁₈ alcohols, and polyoxyethylene (20) C₁₂-C₁₅ alcohols;alcohol alkoxylates including butyl polyoxyethylene/polyoxypropyleneblock copolymer; alkyl polysaccharides including C₈-C₁₁alkylpolysaccharides; glycerol oleate; polyoxyethylene-polyoxypropyleneblock copolymers of MW 1100 to 11400 and 10 to 80% EO; nonyl phenolethoxylates including polyoxyethylene (2 to 8) nonylphenol; polymericsurfactants including graft copolymer such as polymethacrylic acid andacrylate with polyoxyethylene chains and random copolymer with ester andether group; polyethylene glycols including MW: 200 to 8000, MW: 400 PEGdioleate, and MW: 600 PEG dioleate; sorbitan fatty acid esterethoxylates including polyoxyethylene (20) sorbitan tristearate,polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (5) sorbitanmonooleate, and polyoxyethylene (20) sorbitan trioleate; and mixturesthereof; preparing a second composition being the polychlorinated (CuII) phthalocyanine dispersed in water; adding the silicone surfactant toone or both of the first and second compositions; and thereafter priorto use; and mixing an effective amount of the first composition with aneffective amount of the second composition, the polychlorinated (Cu II)phthalocyanine being dispersed and stable therein.
 10. The method ofclaim 9 further comprising diluting the mixture of the first and secondcompositions with water for forming the oil-in-water emulsion, whereinthe paraffinic oil portion of the oil-in-water emulsion is delivered tothe turfgrass in a range of about 1 gal/acre (0.093 L/100 m²) to about15 gal/acre (1.395 L/100 m²), a total spray volume of the oil-in-wateremulsion being in a range of about 20 gal/acre (1.86 L/100 m²) to about200 gal/acre (18.6 L/100 m²).
 11. The method of claim 9 furthercomprising: mixing about 25% to about 75% of the effective amount of thefirst composition and about 25% to about 75% of the second composition;and adding about 25% to about 75% of a recommended label rate of achemical fungicide selected from the group consisting of a demethylationinhibitor, methyl benzimidazole carbamate and dicarboximide for formingan enhanced formulation.
 12. The method of claim 11 further comprisingdiluting the enhanced formulation with water for forming theoil-in-water emulsion, wherein the paraffinic oil portion of theoil-in-water emulsion is delivered to the turfgrass in a range of about1 gal/acre (0.093 L/100 m²) to about 15 gal/acre (1.395 L/100 m²), atotal spray volume of the oil-in-water emulsion being in a range ofabout 20 gal/acre (1.86 L/100 m²) to about 200 gal/acre (18.6 L/100 m²).13. A method for preparing the fungicidal formulation of claim 1comprising: preparing a single composition having the paraffinic oil;the suitable emulsifier selected from the group consisting of natural orsynthetic alcohol ethoxylates including polyoxyethylene(4 to 7) laurylether (C₁₂); polyoxyethylene (10) cetyl ether (C₁₆); polyoxyethylene (2to 11) C₁₂-C₁₅ alcohols; polyoxyethylene (3 to 9) C₁₁-C₁₄ alcohols;polyoxyethylene (9) C₁₂-C₁₄ alcohols; polymeric surfactants includinggraft copolymer such as polymethacrylic acid and acrylate withpolyoxyethylene chains; and random copolymer with ester and ether group;sorbitan fatty acid esters including sorbitan tristearate; and sorbitantrioleate; and mixtures thereof; the polychlorinated (Cu II)phthalocyanine being a dispersed in oil; and the silicone surfactant,wherein the silicone surfactant further comprises polyethylene glycols(PEG) according to Formula (IV):R₁—O—(CH₂—CH₂—O)_(n)—R₂  Formula (IV) where: R₁═H or CH₂═CH—CH₂ or COCH₃14. The method of claim 13 further comprising diluting the singlecomposition with water for forming the oil-in-water emulsion, whereinthe paraffinic oil portion of the oil-in-water emulsion is delivered tothe turfgrass in a range of about 1 gal/acre (0.093 L/100 m²) to about15 gal/acre (1.395 L/100 m²), a total spray volume of the oil-in-wateremulsion being in a range of about 20 gal/acre (1.86 L/100 m²) to about200 gal/acre (18.6 L/100 m²).
 15. The method of claim 13 furthercomprising: mixing about 25% to about 75% of the single composition; andadding about 25% to about 75% of a recommended label rate of a chemicalfungicide selected from the group consisting of a demethylationinhibitor, methyl benzimidazole carbamate and dicarboximide for formingan enhanced formulation.
 16. The method of claim 15 further comprisingdiluting the enhanced formulation with water for forming theoil-in-water emulsion, wherein the paraffinic oil portion of theoil-in-water emulsion is delivered to the turfgrass in a range of about1 gal/acre (0.093 L/100 m²) to about 15 gal/acre (1.395 L/100 m²), atotal spray volume of the oil-in-water emulsion being in a range ofabout 20 gal/acre (1.86 L/100 m²) to about 200 gal/acre (18.6 L/100 m²).